Photographic color picture



Patented Sept. 10, 1940 Wilhelm Schneider and Germany, assignors,

General Aniline & Film Corporation,-

N. Y., a corporation of Delaware No Drawing. Application April 3, 1939, Serial No. 265,758. In GermanyApril 9, 1938 8Claims. (0195-6) Our present invention relates to the manufacture of photographic color pictures.

It is known that photographicv color pictures can-be produced with the aid of color developmentby introducinginto the developer or into the photographic layer a color former which condenses with certain developer substances-to produce a color on thesilver image. As dyestuff formers for color development-there have been proposed among others aliphatic and aromatic acid methylene compounds, for example ethylacetoacetate and its derivatives, ethylbenzoylacetate, pyrazolones or the like. 1 A

This one object'of ourinvention to provide a processof the kind in'question in which there are used for color development pyroracemic acids and derivatives of pyroracemic acids in which the .methyl group contains as a. substituent a radicle of aliphatic, isocyclicor heterocyclic nature, having double linking adjacent to said methyl group. Vinylene groups may be substituted,

further object of this invention is the provision of compounds having the following general formula 1.

. R1-'CI-I2-CO R2 inflwhich R1 is a radicle. of acyclic, .isocyclic or heterocyclic nature which has one or more double linkings adjacent to the CI-Iz-group and may contain-substituents, for instance methyl, carboxyl or the like, and R2 is carboxyl, a substituted carboxyl, ON or the like.

Other objects vof our invention, will become apparent from the following detailed description. For example the following compounds may be used: oxalocrotonic acid diethyl ester, oxalosorbic 891d diethyl ester, quinolyl-pyroracemic acid. The color formers may be. added either to the photographic developer or to the emulsion.. With color develop-. ers, for example pararivative thereof yellow, orange or red dyestufi images are obtained. incorporated in the photographic layer it is, to

be recommended that it should be made fast to.

diffusion with respect to the binding agent of the layer, by the introduction of special groups.v For information about such groups the following UL 2,179,238, 2,178,612, 2,186,849, 2,186,733, 2,186,851, ,186,719, 191,952, filed S. Patent Nos. 2,179,244, 2,186,732, 2,186,852, and application Ser.v No.

February 23, 1938, may be consulted. Y The group that is to impart fastness to diffusion may be introduced into the molecule of the color phenyl-pyroracemic acid,

henylenediamine or a de-' When the color former is former in the manner described in applications b methods; or the color former to dilfusion by said applications.

Hermann 'Lohaus, Dessau, by mesne assignments, to New York,

the foregoing y means of the usual chemical may be made fast polymerization as described inthe The silver halide emulsion containing color formers fast to diffusion may be' used in known manner single layer or sion layers may for making photographic multilayer material. The emulalso be made by distributing dif-' ferently sensitized emulsions having different color formers in the support.

form'of small particles on a produced in various manners, for example as described'in the U. S.

Patent Nos.

111,250, filed November 2,179,228, 2,179,238, 2,186,849, 6,730, and application Ser. 'No.

17, 1936. The image may be produced in the exposed emulsion layer by simple color development or by'reversal developthe U. S. Patent applications Ser.'No. 148,731, filed June 17, 1937, and U. S. Patent No. 2179,23 1.

In producing ,the aid of silver inaccordance be removed or black and wh'te pictures with halide emulsion layers produced with the invention the silver may may be left' in the layer with the dyestuff image.

The following tion Example 1.-To

examples illustrate the inven- 1 kilo of a silver halide emulsion 5 grams of the sodium salt of phenylpyro-' racemic acid of the formula CsH5-CHa-COCOOH are added and the emulsion is cast to form a layer.

The exposed layer yields on development withpara-dimethylaminoaniline a yellow dyestuff image.

Example 2.-To 1 kilo of a silver halide emulsion there are formula added 5 grams of the sodium salt ester of the exposed layer yields on development with paradimethylaminoaniline a yellow dyestufi image. Example 3.-To 1 kilo of a silver halide emulsion there are added 5 grams the oxalosorbic acid of the sodium salt of diethyl ester of the formula cH-wm-omcoocnin and the emulsion is cast to form a layer. The

exposed layer yields on development with paradiethylaminoaniline image.

Example 4.To 1 kilo of a silver halide emulsion 5 grams of oxalomethylcrotonic acid ethyl 5 ester are added and the emulsion is cast to form a layer. The exposed layer yields on development with .para-diethylaminoaniline' a reddish yellow dyestufi image. I

Example 5.- To 1 kilo of a silver halide emulan orange-red dyestufi of ortho-nitrophenyl-pyroracemic acid. and the. emulsion is cast to form a layer;

aminoaniline a red dyestuifimage. v

Example 6.To 1 kilo of. asilven halide-emul;--

sion there are added 5 grams of the sodium saltof para-nitrophenyl-pyroracemic acid. and the emulsion is cast to form a layer. The exposed;

layer yields on development withpara-diethylaminoaniline a red dyestuff image.

Example 7..-T.o-1 kilo of a silver halide emul-.

353 pyroracemic acidethyl ester and the. emulsionv is.cast to-form a layer. The exposed layer yields on. development with para-diethylaminoaniline a yellow dyestufi image.

Example 1.0.4-aminophenyl-pyroracemic acid is.caused; toreact in pyridine with stearic acid chloride fand the 4 stearoylarninophenyl-racemic acid thus obtained is precipitated. by meansv of' dilute acid. 5 grams of. this. product are added to 1. kilo. of. a silver halide emulsion .and the emulsion-is cast. to form aflayer. Tliefexposed' layer yields on development with para-diethylaminoaniline a yellow dyestuif image.

Example 11-.+4.eaminophenyl-racemic acid is caused to react in pyridine withll l' diphenyl- 5Q; dicarboxylic. acid chloride and the product is. pre-' cipitated;.. 51 grams. of the product obtained are added to lkilo of'a silver halide emulsionand the emulsion is cast to form a layer. The exposed emulsion yields on development with para-diethylaminoaniline a. yellow dyestufi image.

Example 12.-To 1. kilo of aisilver halide emule sionthere. are added. 5 grams of quinoxalyl-Z- pyroracemic acid ethyl ester corresponding with the formula I CCH2.C 0.0 O 0 CZHE m ing with the formula sion there are added 5 grams of the sodium salt:

The exposedlayer yields on development. with para-diethyl-- The exposed and the emulsion is cast to form a layer. The exposed layer yields on development with para-diethylaminoaniline an orange dyestufi image.

Example 14.To 1 kilo of a silver halide emulsion there are added 5 grams of benzoxazole-2- pyroracemic acid corresponding with the formula CCH2.C 0.0 OOH N andthe emulsion is cast to form a layer. The exposed-layer yields.) on development with para-diethylaminoanilinaan. orange dyestufi image.

Exam'pZe'15.-To'-1= kilo of a silver halide emulsion-there-are added5 grams of benzthiazole-Z pyroracemic acid corresponding with the formula substituted by an organic radicle having. an...

unsaturated double: bond; in. a. position adjacent: to the carbon atom of .said;methyl.group,-.to.react with the-oxidation: product or. an aromatic: deeveloper. 1

2;. In a process of producing v a'. photographic: color picture by dyestufi' formingidevelopment; the improvement Whichcomprisesacausing asithea dyestuff former a compoundri corresponding: with.

the 1 following general;fonnu1a'.E;iCH2;.-CO I-Rq, in which R1 is a radicle selected from the classconsisting ofran'yaliphatic radiclej. an; i'socyclio radicle and aheterocyclic. radicle, saidradicla having an unsaturated double bond adjacent'itos said CI-Iz-group, R2 isaradicle selected from the class consisting of carboxyl; substituted carboxyl, and UN; .to .reaouwith the oxidation-productof anc aromatic developer. I 1

3; In a: process of producing a photographiecolor picture by dyestuff' forming development, the improvement which comprises developin'gthe exposed photographic silver halide-emulsiomwith an. aromatic amino developer containing asthe dyestuif" former a: derivative of the pyroracemic acid; at leastthe methyl-'group-of said acid being substituted byan organic 'radicle havinganun saturated double loondin a position adjacent'to the carbon atom of'said methyl group; 7

4. In a process offproducing a: photographic' color picture by dyestufi forming development; the improvement which: comprises exposing. a photographic silver halide emulsion containing! as the dyestufi former a' derivative-ofthe. py roracemic acid, at'least-the methyl g1'oup=ofsaid.- acid being substitut'edby-an.organic'radicle hav ing an unsaturateddoublebond in a. position: ad jacent to the carbon atom of said methyligroup; and: developing' said emulsion with an aromaticamino developen' Y r l 5. In atprocess -of producing" a photographic color picture by dyestuif forming development} the improvementwhichcomprises exposing a photographic silver halide emulsion containing asthe dyestuifi-former a derivative of the pyjacent to the carbon atom of said methyl group,

said derivative containing a radicle imparting thereto fastness to diffusion with respect to the binding agent of said emulsion, and developing said emulsion with an aromatic amino developer.

6. Silver halide emulsion for color photography comprising a derivative of the p-yroracemic acid, at least the methyl group of said acid being substituted by an organic radicle having an unsaturated double bond in a position adjacent to the carbon atom of said methyl group, said derivative containing a radicle imparting thereto fastness to diffusion with respect to the binding agent of said emulsion.

7. A dyestuif forming developer comprising an aqueous solution containing an aromatic amino developing agent and a derivative of the p yroracemic acid, at least the methyl group: of said acid being substituted by an organic radicle having an unsaturated double bond in a position 1 adjacent to the carbon atom of said methyl group. p

8. A silver halide emulsion for color photography containing as a color-forming development component a derivative of pyroracemic acid of the following general formula wherein R1 is an organic radicle, having an unsaturated double bond in a position adjacent to the WILI'IELM SCHNEIDER.

HERMANN LOHAUS. 

